US20240327325A1 - Method for producing aldehyde, method for producing alcohol, and catalyst composition - Google Patents

Method for producing aldehyde, method for producing alcohol, and catalyst composition Download PDF

Info

Publication number
US20240327325A1
US20240327325A1 US18/743,198 US202418743198A US2024327325A1 US 20240327325 A1 US20240327325 A1 US 20240327325A1 US 202418743198 A US202418743198 A US 202418743198A US 2024327325 A1 US2024327325 A1 US 2024327325A1
Authority
US
United States
Prior art keywords
catalyst
group
producing
aldehyde
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
US18/743,198
Other languages
English (en)
Inventor
Masashi Miyake
Takashi Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Assigned to MITSUBISHI CHEMICAL CORPORATION reassignment MITSUBISHI CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SATO, TAKASHI, MIYAKE, MASASHI
Publication of US20240327325A1 publication Critical patent/US20240327325A1/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4092—Regeneration or reactivation of catalysts containing metals involving a stripping step, with stripping gas or solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • the present invention relates to a method for producing an aldehyde, a method for producing an alcohol, and a catalyst composition.
  • the hydroformylation reaction is also called an “oxo reaction”.
  • a mixed gas of hydrogen (H 2 ) and carbon monoxide (CO) to be used in the reaction is called an “oxo gas”.
  • the catalyst used for the hydroformylation reaction of an olefin contains an expensive periodic table Group 8 to 10 metal such as rhodium, and it is therefore ideal to use the catalyst semipermanently. Accordingly, a method in which the reaction product is separated from the reaction solution and the reaction solution containing the catalyst as a distillation residue is circulated to a reaction zone and reused, or a method in which the reaction product is distilled off and separated from a reaction zone by using gas stripping and the reaction is continuously performed while allowing the catalyst-containing reaction solution to remain in the reaction zone, is usually employed.
  • a high-boiling-point byproduct such as an aldehyde condensation byproduct is produced and accumulated, making it necessary to withdraw part of the reaction solution continuously or intermittently outside the reaction zone (the reaction zone may be referred to as a reaction system). Since the withdrawn reaction solution contains a catalyst, in particular, an expensive periodic table Group 8 to 10 metal in addition to the high-boiling-point byproduct, it is extremely important to efficiently recover the catalyst in terms of economy and prevention of environmental pollution.
  • Patent Literature 1 describes a method in which a hydroformylation reaction solution having accumulated therein a high-boiling-point byproduct and withdrawn from a reaction zone is mixed with an alcohol and water, and the mixture is brought into contact with a hydrogen gas at 30° C., and then cooled to 0° C., thereby crystallizing and recovering a hydrogen-coordinated rhodium-phosphine complex catalyst.
  • Patent Literature 2 describes a method in which a hydroformylation reaction solution having accumulated therein a high-boiling-point byproduct and withdrawn from a reaction zone is mixed with an alcohol, water, and hydrogen, followed by maintaining at 10° C. to 30° C., thereby precipitating and recovering a hydrogen-coordinated rhodium-phosphine complex catalyst.
  • Patent Literature 3 describes a method in which an alkyl phosphine produced by partially substituting a ligand such as triarylphosphine with an alkyl group of a-olefin is treated with a sufficient amount of oxygen or an oxygen-containing gas at about 20° C. to 80° C. and converted to its corresponding phosphine oxide and the deactivated catalyst is thereby reactivated.
  • a ligand such as triarylphosphine
  • an oxygen-containing gas at about 20° C. to 80° C.
  • Patent Literature 4 describes a method in which a hydroformylation reaction solution having accumulated therein a high-boiling-point byproduct and withdrawn from a reaction zone is mixed with an alcohol and water, and the mixture is brought into contact with a hydrogen gas at 30° C., and then cooled to 0° C., thereby crystallizing and recovering a hydrogen-coordinated rhodium-phosphine complex catalyst.
  • Patent Literature 1 WO2019-098242
  • Patent Literature 2 JP2006-151826A
  • Patent Literature 3 JPS57-87845A
  • Patent Literature 4 JPS57-122948A
  • Patent Literatures 1 to 4 first, it is necessary to crystallize a rhodium-phosphine complex catalyst in a state in which a high-boiling-point byproduct is removed as much as possible to recover as a crystal having no adhesiveness, and then to separate the crystal of the rhodium-phosphine complex catalyst from a crystallized mother liquid by subjecting the recovered crystal to a filtration treatment.
  • Patent Literatures 1 to 4 since the loss of the rhodium-phosphine complex catalyst in the filtration treatment is large, the rhodium-phosphine complex catalyst cannot be sufficiently recovered.
  • An object of the present invention is to solve the problems.
  • An object of the present invention is to provide a method for producing an aldehyde capable of recovering, from a hydroformylation reaction solution, an expensive complex catalyst, in particular, an expensive periodic table Group 8 to 10 metal in a complex catalyst at a high yield.
  • An object of the present invention is to provide a method for producing an alcohol in which an aldehyde is produced by the method for producing an aldehyde, followed by producing an alcohol from the aldehyde.
  • an object of the present invention is to provide a catalyst composition capable of recovering an expensive complex catalyst to be used in a reaction such as a hydroformylation reaction, in particular, an expensive periodic table Group 8 to 10 metal in a complex catalyst at a high yield.
  • the present inventors have found that a complex catalyst can be recovered at a yield higher than that in a method of related art by mixing a reaction solution after a hydroformylation reaction with a poor solvent for a catalyst, performing an aggregation treatment in a state of containing the catalyst and a high-boiling-point byproduct, and recovering an aggregate having adhesiveness.
  • the present invention has been achieved based on such findings, and the gist thereof is as follows.
  • a method for producing an aldehyde including:
  • a distribution ratio of the high-boiling-point byproduct contained in the aggregate is 4.0 mass % or more.
  • the part or all of the reaction solution is mixed with the poor solvent for the catalyst in a mixing tank, and the precipitated aggregate adheres to an inner surface of the mixing tank, or is settled in an aggregated state in the mixing tank.
  • a method for producing an aldehyde including:
  • a distribution ratio of the high-boiling-point byproduct contained in the aggregate is 4.0 mass % or more.
  • the part or all of the reaction solution is mixed with the poor solvent for the catalyst in a mixing tank, and the precipitated aggregate adheres to an inner surface of the mixing tank, or is settled in an aggregated state in the mixing tank.
  • a method for producing an aldehyde including:
  • the aggregate has adhesiveness under the precipitation condition.
  • a distribution ratio of the high-boiling-point byproduct in the aggregate is 4.0 mass % or more.
  • the precipitated aggregate is fed to a hydroformylation reaction zone.
  • the precipitated aggregate is dissolved in a good solvent for the catalyst and fed to the hydroformylation reaction zone.
  • the precipitation is performed under neutral to acidic conditions.
  • the catalyst is a periodic table Group 8 to 10 metal-organophosphorus complex catalyst.
  • the catalyst is a periodic table Group 8 to 10 metal-phosphite complex catalyst.
  • the periodic table Group 8 to 10 metal is rhodium.
  • the poor solvent contains water and an alcohol.
  • the poor solvent is a mixture of water and an alcohol, and a content ratio of the water is 12 mass % to 40 mass % with respect to 100 mass % of a total mass of the mixture.
  • the aggregate is precipitated under a condition of a temperature of 0° C. or higher and 70° C. or lower.
  • a method for producing an alcohol including:
  • a catalyst composition containing:
  • the catalyst is a periodic table Group 8 to 10 metal-organophosphorus complex catalyst
  • a content ratio of the high-boiling-point byproduct is 30 mass % or more, based on 100% of a total mass of the catalyst composition.
  • the catalyst composition has adhesiveness.
  • the catalyst is a catalyst for producing an aldehyde by subjecting an olefin to a hydroformylation reaction.
  • the catalyst is a periodic table Group 8 to 10 metal-phosphite complex catalyst.
  • the periodic table Group 8 to 10 metal is rhodium.
  • a method for producing an aldehyde including:
  • a method for producing an aldehyde capable of recovering, from a hydroformylation reaction solution, a complex catalyst, in particular, an expensive periodic table Group 8 to 10 metal in a complex catalyst at a high yield can be provided.
  • a method for producing an alcohol using an aldehyde produced by the method for producing an aldehyde can also be provided.
  • a catalyst composition recovered by the above-described method for producing an aldehyde can be provided.
  • FIG. 1 is a graph showing a relationship between a distribution ratio of a high-boiling-point byproduct in an aggregate or a crystallized product and a rhodium recovery ratio in Examples 1 to 10 and Comparative Example 1.
  • FIG. 2 A is an appearance photograph of a mixing tank after aggregation, which is obtained in Example 2, and is an example of a state in which aggregates adhere to an inner surface of the mixing tank and a reaction solution after reaction is solid-liquid separated, and
  • FIG. 2 B is an appearance photograph of a mixing tank after crystallization, which is obtained in Comparative Example 1, and is an example of a state in which a crystallized product does not adhere to an inner surface of the mixing tank and a reaction solution after reaction is not solid-liquid separated and forms a uniform slurry.
  • a numerical range expressed using “to” means a range that includes numerical values written before and after “to” as an upper limit value and a lower limit value.
  • a to B means A or more and B or less.
  • a first embodiment of a method for producing an aldehyde of the present invention is a method for producing an aldehyde including: subjecting an olefin to a hydroformylation reaction with a gas containing hydrogen and carbon monoxide in the presence of a catalyst (hereinafter, the step may be referred to as a “hydroformylation reaction step”); and mixing part or all of a reaction solution withdrawn from a reaction zone (hereinafter, the step may be referred to as a “reaction solution withdrawing step”) with a poor solvent for the catalyst to precipitate an aggregate containing the catalyst and having adhesiveness (hereinafter, the step may be referred to as an “aggregation step”).
  • a distribution ratio of the high-boiling-point byproduct contained in the aggregate is preferably 4.0 mass % or more.
  • the part or all of the reaction solution is mixed with the poor solvent for the catalyst in a mixing tank, and the precipitated aggregate may adhere to an inner surface of the mixing tank, or may be settled in an aggregated state in the mixing tank.
  • a second embodiment of the method for producing an aldehyde of the present invention is a method for producing an aldehyde including: subjecting an olefin to a hydroformylation reaction with a gas containing hydrogen and carbon monoxide in the presence of a catalyst (hereinafter, the step may be referred to as a “hydroformylation reaction step”); and mixing part or all of a reaction solution withdrawn from a reaction zone (hereinafter, the step may be referred to as a “reaction solution withdrawing step”) with a poor solvent for the catalyst to precipitate an aggregate containing the catalyst (hereinafter, the step may be referred to as an “aggregation step”), in which when a total mass of a high-boiling-point byproduct contained in the reaction solution is 100 mass %, a distribution ratio of the high-boiling-point byproduct contained in the aggregate is preferably 4.0 mass % or more.
  • the part or all of the reaction solution is mixed with the poor solvent for the catalyst in a mixing tank, and the precipitated aggregate may adhere to an inner surface of the mixing tank, or may be settled in an aggregated state in the mixing tank.
  • a third embodiment of the method for producing an aldehyde of the present invention is a method for producing an aldehyde including: subjecting an olefin to a hydroformylation reaction with a gas containing hydrogen and carbon monoxide in the presence of a catalyst (hereinafter, the step may be referred to as a “hydroformylation reaction step”); withdrawing part or all of a reaction solution having accumulated therein a high-boiling-point byproduct from a reaction zone (hereinafter, the step may be referred to as a “reaction solution withdrawing step”); mixing the withdrawn reaction solution with a poor solvent for the catalyst in a mixing tank to precipitate an aggregate containing the catalyst and the high-boiling-point byproduct (hereinafter, the step may be referred to as an “aggregation step”); and adhering the precipitated aggregate to an internal surface of the mixing tank and recovering the aggregate (hereinafter, the step may be referred to as a “recovery step”).
  • the precipitate when the reaction solution withdrawn from a hydroformylation reaction zone is mixed with the poor solvent for the catalyst, an adhesive precipitate containing the catalyst and the high-boiling-point byproduct is precipitated as shown in Examples to be described later. Since the precipitate is adhesive and is not in a crystalline state, the precipitate cannot be sufficiently expressed by the term “crystallized product”, and therefore, in the present invention, the precipitate is referred to as an “aggregate” and is distinguished from a non-adhesive precipitate precipitated by a method of related art or in Comparative Example to be described later. On the other hand, the non-adhesive precipitate precipitated by the method of the related art and in Comparative Example to be described later is referred to as a “crystallized product”.
  • a tank in which the reaction solution and the poor solvent for the catalyst are mixed is referred to as a “mixing tank”, “precipitation” of “aggregate” in the “mixing tank” is referred to as an “aggregation treatment”, and the step is referred to as an “aggregation step”.
  • the “inner surface of the mixing tank” refers to a portion where a flow of the reaction solution is slow in the mixing tank, a portion where the aggregate in the reaction solution is pressed during stirring, or a portion having a shape of a protrusion in the mixing tank, and specific examples thereof include a bottom surface or an inner wall of the mixing tank, a baffle, a stirring blade or a stirring shaft, and a surface of a side pipe.
  • reaction zone and the “hydroformylation reaction zone” refer to a zone including a reactor for performing the hydroformylation reaction and reactor peripheral equipment such as a gas-liquid separator attached to the reactor.
  • a catalyst composition of the present invention contains: a catalyst; and a high-boiling-point byproduct.
  • the catalyst is a periodic table Group 8 to 10 metal-organophosphorus complex catalyst.
  • a content ratio of the high-boiling-point byproduct is 30 mass % or more, based on 100% of a total mass of the catalyst composition.
  • the present invention a hydroformylation reaction according to the first, second, and third embodiments of the method for producing an aldehyde of the present invention (hereinafter may be collectively referred to as “the present invention”) will be described, and subsequently, the reaction solution withdrawing step, the aggregation step, and the recovery step will be described for each step.
  • the catalyst used for the hydroformylation reaction is not particularly limited as long as it has a catalytic effect on the hydroformylation reaction of an olefin.
  • the catalyst used for the hydroformylation reaction it is preferable to use a periodic table Group 8 to 10 metal (hereinafter referred to as “Group 8 to 10 metal”)-organophosphorus complex catalyst because of excellent reaction activity thereof.
  • the Group 8 to 10 metal is a metal belongs to Groups 8 to 10 in the periodic table.
  • ruthenium, cobalt, rhodium, palladium, and platinum are preferred since they have high activity in case of use as a catalyst, and in particular, rhodium is preferably used since it has high activity.
  • any trivalent organophosphorus compound that commonly functions as a monodentate ligand or a polydentate ligand for the Group 8 to 10 metal can be used.
  • examples of the organophosphorus compound serving as a monodentate ligand include a tertiary triorganophosphine represented by the following formula (I).
  • R's each independently represent a substituted or unsubstituted monovalent hydrocarbon group.
  • Examples of the monovalent hydrocarbon group represented by R usually include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 3 to 12 carbon atoms, an alkylaryl group having 6 to 24 carbon atoms, and an arylalkyl group having 6 to 24 carbon atoms.
  • examples of the above-described triorganophosphine include trialkylphosphine, triarylphosphine, tricycloalkylphosphine, alkylarylphosphine, cycloalkylarylphosphine, and alkylcycloalkylphosphine.
  • a substituent that the monovalent hydrocarbon group may have is not particularly limited, and examples thereof include an alkyl group and an alkoxy group.
  • triorganophosphine examples include tributylphosphine, trioctylphosphine, triphenylphosphine, tritolylphosphine, tricycloalkylphosphine, monobutyldiphenylphosphine, dipropylphenylphosphine, and cyclohexyldiphenylphosphine.
  • triphenylphosphine is preferred because of low activity, chemical stability, and easy availability.
  • trivalent organophosphorus compound for example, a trivalent phosphite compound represented by the following formulae (1) to (10) can be used.
  • R 1 to R 3 each independently represent a monovalent hydrocarbon group which may have a substituent.
  • Examples of the monovalent hydrocarbon group which may have a substituent and is represented by R 1 to R 3 include an alkyl group, an aryl group, and a cycloalkyl group.
  • the compound represented by the formula (1) include trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, n-butyl diethyl phosphite, tri-n-butyl phosphite, tri-n-propyl phosphite, tri-n-octyl phosphite, and tri-n-dodecyl phosphite, triaryl phosphites such as triphenyl phosphite and trinaphthyl phosphite, and alkylaryl phosphites such as dimethylphenyl phosphite, diethylphenyl phosphite, and ethyldiphenyl phosphite.
  • trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, n-butyl diethyl pho
  • bis (3,6,8-tri-t-butyl-2-naphthyl) phenylphosphite and bis (3,6,8-tri-t-butyl-2-naphthyl) (4-biphenyl) phenylphosphite described in JPH6-122642A may be used.
  • triphenyl phosphite is most preferred.
  • R 4 represents a divalent hydrocarbon group which may have a substituent.
  • R 5 represents a monovalent hydrocarbon group which may have a substituent.
  • Examples of the divalent hydrocarbon group which may have a substituent for R 4 include an alkylene group which may contain oxygen, nitrogen, a sulfur atom, etc. in the middle of a carbon chain, a cycloalkylene group which may contain oxygen, nitrogen, a sulfur atom, etc. in the middle of a carbon chain, a divalent aromatic group such as phenylene and naphthylene, a divalent aromatic group to which a divalent aromatic ring is bonded directly or intermediately through an alkylene group or an atom such as oxygen, nitrogen, or sulfur; and a group to which a divalent aromatic group and an alkylene group are bonded directly or intermediately through an atom such as oxygen, nitrogen, or sulfur.
  • an alkylene group which may contain oxygen, nitrogen, a sulfur atom, etc. in the middle of a carbon chain
  • a cycloalkylene group which may contain oxygen, nitrogen, a sulfur atom, etc. in the middle of a carbon chain
  • a divalent aromatic group such as
  • Examples of the monovalent hydrocarbon group for R 5 include an alkyl group, an aryl group, and a cycloalkyl group.
  • Examples of the compound represented by the formula (2) include compounds described in U.S. Pat. No. 3,415,906 specification, such as neopentyl (2,4,6-t-butyl-phenyl) phosphite, and ethylene (2,4,6-t-butyl-phenyl) phosphite.
  • R 10 has the same meaning as R 5 in the above formula (2).
  • Ar 1 and Ar 2 each independently represent an aryl group which may have a substituent.
  • x and y each independently represent 0 or 1.
  • Q is a crosslinking group selected from the group consisting of —CR 11 R 12 —, —O—, —S—, —NR 13 —, —SiR 14 R 15 and —CO—.
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, or an anisyl group.
  • R 13 , R 14 and R 15 each independently represent a hydrogen atom or a methyl group.
  • n represents 0 or 1.
  • trivalent phosphite compound represented by the formula (3) examples include compounds described in U.S. Pat. No. 4,599,206 specification, such as 1,1′-biphenyl-2,2′-diyl-(2,6-di-t-butyl-4-methylphenyl) phosphite, and compounds described in U.S. Pat. No. 4,717,775 specification, such as 3,3′-di-t-butyl-5,5′-dimethoxy-1,l′-biphenyl-2,2′-diyl (2-t-butyl-4-methoxyphenyl) phosphite.
  • R 6 represents a trivalent hydrocarbon group which may have a cyclic or acyclic substituent.
  • Examples of the compound represented by the formula (4) include compounds described in U.S. Pat. No. 4,567,306 specification, such as 4-ethyl-2,6,7-trioxa-1-phosphabicyclo-[2,2,2]-octane.
  • R 7 has the same meaning as R 4 in the above formula (3).
  • R 8 and R 9 each independently represent a hydrocarbon group which may have a substituent.
  • a and b each represent an integer of 0 to 6. The sum of a and b is 2 to 6.
  • X represents a (a+b)-valent hydrocarbon group.
  • Preferred examples of the compound represented by the formula (5) include a compound represented by the following formula (6).
  • Compounds described in JPS62-116535A and JPS62-116587A are included.
  • X represents a divalent group selected from the group consisting of alkylene, arylene, and —Ar 1 —(CH 2 )x-Qn—(CH 2 )y-Ar 2 —.
  • Ar 1 , Ar 2 , Q, x, y, and n are the same as Ar 1 , Ar 2 , Q, x, y, and n in the above formula (3).
  • R 19 and R 20 each independently represent an aromatic hydrocarbon group, and at least one of the aromatic hydrocarbon groups has a hydrocarbon group at a carbon atom adjacent to a carbon atom to which an oxygen atom is bonded.
  • m represents an integer of 2 to 4.
  • The-OP (OR 19 ) (OR 20 ) groups may be different from each other.
  • X represents an m-valent hydrocarbon group which may have a substituent.
  • R 21 to R 24 each independently represent a hydrocarbon group which may have a substituent.
  • R 21 and R 22 , and R 23 and R 24 may be bonded to each other to form a ring.
  • W represents a divalent aromatic hydrocarbon group which may have a substituent.
  • L represents a saturated or unsaturated divalent aliphatic hydrocarbon group which may have a substituent.
  • R 25 to R 28 each represent a monovalent hydrocarbon group which may have a substituent.
  • R 25 and R 26 , and R 27 and R 28 may be bonded to each other to form a ring.
  • a and B each independently represent a divalent hydrocarbon group which may have a substituent.
  • n represents an integer of 0 or 1.
  • Examples of the monovalent hydrocarbon group which may have a substituent and is represented by R 25 to R 28 include an alkyl group, an aryl group, and a cycloalkyl group.
  • the divalent hydrocarbon group which may have a substituent for A and B may be any of an aromatic group, an aliphatic group, and a alicyclic group.
  • R 31 and R 41 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms.
  • alkyl group having 1 to 20 carbon atoms examples include a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an s-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, a t-hexyl group, and a 1,1,2-trimethylpropyl group.
  • one having 3 to 20 carbon atoms is preferred, one having 4 to 20 carbon atoms is more preferred, and one having 4 to 10 carbon atoms is particularly preferred.
  • one whose carbon atom bonded to an aromatic ring is tertiary is preferred, and examples thereof include a t-butyl group, a t-pentyl group, and a t-hexyl group.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, and an adamantyl group. Among them, a cycloalkyl group having 6 to 14 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred.
  • R 31 and R 41 a tertiary alkyl group having 4 to 20 carbon atoms is preferred, a tertiary alkyl group having 4 to 7 carbon atoms is more preferred, and a t-butyl group is particularly preferred.
  • R 31 and R 41 may be the same as or different from each other.
  • R 31 and R 41 are a t-butyl group
  • a sufficient stabilization effect against hydrolysis of the compound represented by the formula (11) can be obtained due to bulkiness of the t-butyl group.
  • R 31 and R 41 are particularly preferably a t-butyl group.
  • R 32 and R 42 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group and an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group and a cycloalkoxy group having 3 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, an aryl group and an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group, an alkylaryoxy group, an arylalkyl group and an arylalkoxy group having 7 to 20 carbon atoms, a cyano group, a hydroxy group, and a halogen atom.
  • alkyl group having 1 to 20 carbon atoms examples include a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a t-pentyl group, and a t-hexyl group.
  • a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a t-pentyl group,
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, and an adamantyl group.
  • alkoxy group having 1 to 20 carbon atoms examples include a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group. Among them, an alkoxy group having 1 to 12 carbon atoms is preferred.
  • Examples of the cycloalkoxy group having 3 to 20 carbon atoms include a cyclopentyloxy group.
  • dialkylamino group having 2 to 20 carbon atoms examples include a dimethylamino group and a diethylamino group.
  • Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
  • Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group and a naphthoxy group.
  • alkylaryl group having 7 to 20 carbon atoms examples include a p-tolyl group and an o-tolyl group.
  • alkylaryoxy group having 7 to 20 carbon atoms examples include 2,3-xylenoxy.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group.
  • Examples of the arylalkoxy group having 7 to 20 carbon atoms include a 2-(2-naphthyl) ethoxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 32 and R 42 are preferably a hydrogen atom.
  • a substituent at this position has a small contribution to the effect of improving the reactivity with respect to the hydroformylation reaction and the effect of stabilizing the compound represented by the formula (11) itself. Therefore, from the viewpoint of reducing the production cost of the compound, a hydrogen atom, which is the simplest substituent, is preferred.
  • R 33 and R 43 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group and an arylalkyl group having 7 to 20 carbon atoms.
  • alkyl group having 1 to 20 carbon atoms examples include a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an s-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, and a t-hexyl group.
  • one having 4 to 20 carbon atoms is preferred, and one having 4 to 10 carbon atoms is particularly preferred.
  • one whose carbon atom bonded to an aromatic ring is tertiary is preferred, and examples thereof include a t-butyl group, a t-pentyl group, and a t-hexyl group.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, and an adamantyl group. Among them, a cycloalkyl group having 6 to 14 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred.
  • Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
  • alkylaryl group having 7 to 20 carbon atoms examples include a p-tolyl group and an o-tolyl group.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group.
  • R 33 and R 43 are each independently preferably a tertiary alkyl group having 4 to 20 carbon atoms, more preferably a tertiary alkyl group having 4 to 7 carbon atoms, and particularly preferably a t-butyl group.
  • R 34 and R 44 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a silyl group, a siloxy group, and a halogen atom.
  • alkyl group having 1 to 12 carbon atoms examples include a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, and a decyl group.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group and a cyclohexyl group.
  • alkoxy group having 1 to 12 carbon atoms examples include a methoxy group, an ethoxy group, and a t-butoxy group.
  • silyl group examples include a trimethylsilyl group.
  • siloxy group examples include a silyl group and a trimethylsiloxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 34 and R 44 are each independently preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group or an ethyl group, an alkoxy group having 1 to 3 carbon atoms such as a methoxy group or an oxy group, or a halogen atom, and more preferably an alkyl group having 1 to 3 carbon atoms, and R 34 and R 44 are particularly preferably a methyl group.
  • R 34 and R 44 a small alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is particularly preferred. The reason for this is that the hydroformylation reaction can proceed smoothly and the stability of the compound represented by the formula (11) can be improved at the same time.
  • Z 1 to Z 4 are each independently an aryl group having 6 to 20 carbon atoms.
  • the aryl group may have a substituent. Both Z 1 and Z 2 and Z 3 and Z 4 are not bonded to each other.
  • Z 1 to Z 4 each independently have no substituent on an aromatic ring carbon atom adjacent to a carbon atom bonded to an oxygen atom, or have a substituent on the aromatic ring carbon atom, and the number of carbon atoms of the substituent is preferably 0 to 2.
  • the substituent is preferably selected from the group consisting of a group having 1 to 2 carbon atoms such as a methyl group and an ethyl group, a trifluoromethyl group, a cyano group, a nitro group, and a halogen atom such as a chlorine atom and a fluorine atom.
  • examples of the substituent include: a linear or branched alkyl group having 1 to 12 carbon atoms, and preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and a t-pentyl group; an alkoxy group having 1 to 12 carbon atoms, and preferably 1 to 8 carbon atoms, such as a methoxy group and an oxy group; and an aryl group having 6 to 18 carbon atoms, and preferably 6 to 10 carbon atoms, such as a phenyl group and a naphthyl group.
  • substituents include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a hydroxyl group, an amino group, an acyl group, a carbonyloxy group, an oxycarbonyl group, an amide group, a sulfonyl group, a sulfinyl group, a silyl group, and a thionyl group.
  • Z 1 to Z 4 may each have 1 to 5 of the substituents.
  • Z 1 to Z 4 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a p-trifluoromethylphenyl group, a 2-ethylphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2,3-dichlorophenyl group, a 2,4-dichlorophenyl group, a 2,5-dichlorophenyl group, a 3,4-dichlorophenyl group, a 3,5-dich
  • a 1-naphthyl group or a 2-naphthyl group is preferred from the viewpoint of improving the thermal stability of the ligand and improving the selection ratio for producing a linear aldehyde when producing an aldehyde by a hydroformylation reaction.
  • the bisphosphite compound represented by the formula (11) is preferably a bisphosphite compound in which R 31 and R 41 are each independently a tertiary alkyl group having 4 to 20 carbon atoms, R 32 and R 42 are a hydrogen atom, R 33 and R 43 are each independently a tertiary alkyl group having 4 to 20 carbon atoms, and R 34 and R 44 are each independently selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom.
  • a bisphosphite compound in which Z 1 to Z 4 each independently have no substituent on an aromatic ring carbon atom adjacent to a carbon atom bonded to an oxygen atom, or have a substituent having 1 to 2 carbon atoms on the aromatic ring carbon atom, and none of Z 1 to Z 4 are bonded to each other is preferred.
  • the bisphosphite compound represented by the formula (11) is more preferably a bisphosphite compound in which R 31 , R 41 , R 33 , and R 43 are each independently a tertiary alkyl group having 4 to 7 carbon atoms, R 32 and R 42 each are a hydrogen atom, and R 34 and R 44 are each independently an alkyl group having 1 to 3 carbon atoms.
  • a bisphosphite compound in which Z 1 to Z 4 are each independently a 1-naphthyl group or a 2-naphthyl group is more preferred, and a bisphosphite compound in which R 31 , R 41 , R 33 , and R 43 are a t-butyl group and R 34 and R 44 are a methyl group is particularly preferred.
  • the bisphosphite compound represented by the formula (11) can be produced by a method described in WO2019/039565.
  • organophosphorus ligand compounds may be used alone or in combination of two or more thereof, and usually are used alone.
  • the organophosphorus ligand compound is not particularly limited, and is preferably the phosphite compound represented by the formula (10) or the bisphosphite compound represented by the formula (11), and particularly preferably the bisphosphite compound represented by the formula (11), from the viewpoint of excellent reaction activity and thermal decomposition resistance of the catalyst in the hydroformylation reaction.
  • the Group 8 to 10 metal-organophosphorus complex catalyst used in the present invention is preferably a Group 8 to 10 metal-phosphite complex catalyst.
  • the Group 8 to 10 metal-organophosphorus complex catalyst can be more easily prepared by a known complex formation method using a periodic table Group 8 to 10 metal compound (hereinafter, referred to as a “Group 8 to 10 metal compound”) and an organophosphorus ligand compound.
  • the complex may be formed in the reaction zone by feeding the Group 8 to 10 metal compound and the organophosphorus ligand compound to the reaction zone.
  • the organophosphorus ligand compound may be directly introduced into the reaction zone but, considering ease of handling, etc., is preferably introduced after dissolving it in a reaction medium.
  • the Group 8 to 10 metal compound includes, for example, a water-soluble inorganic salt or inorganic complex compound such as rhodium chloride, palladium chloride, ruthenium chloride, platinum chloride, rhodium bromide, rhodium iodide, rhodium sulfate, rhodium nitrate, palladium nitrate, rhodium ammonium chloride and sodium rhodium chloride; and a water-soluble organic acid salt such as rhodium formate, rhodium acetate, palladium acetate, rhodium propionate, palladium propionate and rhodium octanoate.
  • respective metal complex species may also be used. Among them, in view of excellent reaction activity and catalyst cost, rhodium acetate is preferably used.
  • the hydroformylation reaction is performed by reacting an olefin with hydrogen and carbon monoxide in the presence of a catalyst such as a Group 8 to 10 metal-organophosphorus complex catalyst.
  • a carbon number of olefin is not particularly limited, examples thereof include a carbon number of 2 to 20.
  • the olefin having a carbon number of 2 to 20 may be, for example, an a-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene, or an internal olefin such as 2-butene, 2-pentene, 3-hexene and 4-octene.
  • a solvent that dissolves a raw material olefin and a catalyst such as a Group 8 to 10 metal-organophosphorus complex catalyst has a boiling point higher than that of an aldehyde to be produced, and does not inhibit the reaction is preferred.
  • the solvent that can be used in the hydroformylation reaction include: an aromatic hydrocarbon such as benzene, toluene, and xylene; an aliphatic hydrocarbon such as hexane and octane; esters such as butyl acetate and butyl butyrate ester; and ketones.
  • a concentration of the catalyst in the reaction medium is usually 1 mass ppm to 10 mass % in terms of metal atom of a Group 8 to 10 metal, etc., and the organophosphorus ligand compound such as a phosphite compound used as a ligand is usually present in an excessive amount in the reaction medium in order to increase the stability of the complex catalyst.
  • the hydroformylation reaction may be performed under known conditions.
  • the reaction conditions are usually appropriately selected within the following ranges.
  • Carbon monoxide partial pressure 0.01 MPaG to 20 MPaG
  • Hydrogen partial pressure/carbon monoxide partial pressure 0.1 to 10
  • Reaction temperature 60° C. to 200° C.
  • Rh (rhodium) concentration several mass ppm to several mass %
  • an aldehyde having a carbon number of n+1 can be obtained from a raw material olefin having a carbon number of n (n is, for example, an integer of 2 to 20).
  • n is, for example, an integer of 2 to 20.
  • Such an aldehyde includes propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, etc.
  • the aldehyde is obtained as a mixture of a linear form and a branched form.
  • the hydroformylation reaction is performed under the above-described reaction conditions by using usually a flow-type reactor, but a batch-type reactor may also be used.
  • the main flow reaction (which uses the above flow-type reactor) system includes a stripping system and a liquid circulating system.
  • the stripping system is a method in which a reaction solution containing a catalyst is held in a reactor, an olefin and an oxo gas are continuously fed, and the aldehyde produced by the reaction is vaporized within the reactor and taken out of the system.
  • the liquid circulating system is a method in which an olefin, an oxo gas, and a reaction medium containing a catalyst are continuously fed to a reactor and a reaction solution containing the produced aldehyde, the catalyst, the reaction medium, etc. is continuously withdrawn outside the reactor.
  • the reaction solution withdrawn from the reactor is separated into the produced aldehyde and a catalyst-containing reaction solution, for example, by a separation operation such as stripping with an unreacted gas or distillation.
  • the obtained and produced aldehyde is withdrawn outside the system, and the reaction solution containing the catalyst (in the present invention, the reaction solution corresponds to the reaction solution withdrawn in the reaction solution withdrawing step) is usually returned to the reactor and recycled after removing the high-boiling-point byproduct in the reaction solution using a known separation operation such as distillation.
  • the adhesiveness of the obtained aggregate can be controlled by adjusting the content of the high-boiling-point byproduct in the reaction solution in the aggregation step to be described later.
  • reaction solution containing the high-boiling-point byproduct and the catalyst in the present invention, the reaction solution corresponds to the reaction solution withdrawn in the reaction solution withdrawing step is intermittently withdrawn outside the reaction zone.
  • reaction solution corresponds to the reaction solution withdrawn in the reaction solution withdrawing step
  • the amount of the reaction solution withdrawn from the reaction zone, that is, the reactor may be appropriately determined according to the amount of the high-boiling-point byproduct to be produced.
  • the reaction solution when the reaction solution is withdrawn outside the reaction zone, a catalyst in an amount corresponding to the catalyst contained in the withdrawn reaction solution is newly fed to the reaction zone.
  • the amount of catalyst to be newly fed can be reduced by subjecting the withdrawn reaction solution to the aggregation step and returning the reaction solution to the reaction zone.
  • the reaction can be maintained with almost no replenishment.
  • the constituent component of the high-boiling-point byproduct is various and complicated, but is mainly an aldehyde condensate produced by condensation of an aldehyde which is a target product of the hydroformylation reaction.
  • the aldehyde condensate has a boiling point higher than that of the aldehyde to be produced, and is a high-boiling product that cannot be removed by a simple aldehyde distillation step.
  • Such a high-boiling-point byproduct include aldol which is a dimer of the produced aldehyde, an ester compound which is a dimer of the produced aldehyde and is produced by a Tishchenko reaction of the produced aldehyde, an unsaturated aldehyde which is a dehydrated product of the aldol, a saturated aldehyde and a saturated alcohol which are a hydrogenated product of the unsaturated aldehyde, an unsaturated ether which is a dehydrated product of a hemiacetal obtained by a reaction between the produced aldehyde and an alcohol which is a hydrogenated product thereof, an acetal obtained by a reaction between the hemiacetal and the produced aldehyde, and a trimer of the produced aldehyde.
  • aldol which is a dimer of the produced aldehyde
  • an ester compound which is a dimer of the produced aldehyde and is produced by
  • a phosphite or a phosphonate generated by decomposition of a phosphite, and phosphorous acid are present in the reaction solution having accumulated therein the high-boiling-point byproduct.
  • rhodium when rhodium is used as the Group 8 to 10 metal, the following rhodium complexes (a) and (b) are present in the reaction solution having accumulated therein the high-boiling-point byproduct.
  • the reaction solution withdrawing step is a step of withdrawing part or all of the reaction solution having accumulated therein the high-boiling-point byproduct from the hydroformylation reaction zone, and specifically, a step of withdrawing the reaction solution containing the aldehyde generated by the hydroformylation reaction, the catalyst, and the reaction medium outside the reactor while performing the hydroformylation reaction as described above.
  • the reaction solution in the hydroformylation reaction zone contains about 40 mass % to 80 mass % of the high-boiling-point byproduct.
  • a poor solvent for the catalyst is added to and mixed with the reaction solution containing the high-boiling-point byproduct in the aggregation step to crystallize an aggregate containing the catalyst and the high-boiling-point byproduct.
  • Patent Literatures 1 to 4 as compared with a method of separating a crystal of a catalyst from a crystallized mother liquid by performing crystallization in a state where the high-boiling-point byproduct is removed as much as possible and subjecting the precipitated crystal to a filtration treatment, the loss of the catalyst in the filtration treatment can be eliminated, and the catalyst can be recovered at a high recovery ratio.
  • the hydroformylation reaction solution withdrawn from the hydroformylation reaction zone may be subjected to the aggregation step after removing a light-boiling-point component in the reaction solution.
  • known separation operations such as distillation can be used.
  • the reaction solution withdrawn in the reaction solution withdrawing step that is, the reaction solution before an aggregation treatment, usually has the following composition, and the reaction solution is subjected to the following aggregation step.
  • Rhodium atoms in complex catalyst 50 mass ppm to 2000 mass ppm
  • Phosphite compound 1000 mass ppm to 3 mass %
  • n-Aldehyde 1 mass % to 30 mass %
  • variable complexes contained in the “other components” refer to the various rhodium complexes contained in the reaction solution having accumulated therein the high-boiling-point byproduct, as listed in the section of [Hydroformylation Reaction Step] above.
  • the poor solvent for the catalyst (hereinafter, may be simply referred to as a “poor solvent”) is added to and mixed with the reaction solution withdrawn in the reaction solution withdrawing step to precipitate an aggregate containing the catalyst and the high-boiling-point byproduct.
  • the withdrawn reaction solution and the poor solvent are put into a mixing tank to precipitate an aggregate.
  • the poor solvent is a solvent in which the Group 8 to 10 metal compound has smaller solubility than in the reaction solution.
  • the poor solvent is preferably a solvent that keeps a homogeneous phase with the reaction solution and does not participate in the reaction in the reaction zone.
  • the poor solvent examples include methanol, ethanol, propanol (n-, i-), butanol (n-, i-, t), acetone, and a mixture of acetone and water.
  • a mixture of water and an alcohol is preferred, and a mixture of water and an alcohol having 1 to 3 carbon atoms is particularly preferred.
  • a content ratio of water in the mixture is preferably 12 mass % to 40 mass %, more preferably 13 mass % to 25 mass %, and still more preferably 15 mass % to 22 mass % with respect to 100 mass % of the mixture.
  • a mixing ratio (a mass ratio) of the poor solvent and the reaction solution is preferably 5:1 to 15:1, more preferably 6:1 to 10:1, and still more preferably 7:1 to 9:1, depending on the type of the poor solvent and the composition of the reaction solution.
  • the ratio of the poor solvent is equal to or less than the upper limit, the amount of the complex catalyst dissolved in the poor solvent decreases, the recovery ratio of the catalyst increases, and an aggregate recovery device can be reduced in size.
  • the ratio of the poor solvent is equal to or more than the lower limit, the reaction solution tends to become a homogeneous phase, and the recovery ratio of the complex catalyst can be satisfactorily maintained.
  • the withdrawn reaction solution may be directly mixed with the poor solvent or may be mixed with the poor solvent after removing at least part of the reaction medium by distillation, etc.
  • reaction solution and the poor solvent are preferably mixed under stirring.
  • a temperature in the aggregation step is preferably 0° C. to 70° C., more preferably 0° C. to 40° C., and further preferably 5° C. to 20° C.
  • the temperature during aggregation is equal to or lower than the upper limit, the recovery ratio of the catalyst is excellent.
  • the temperature during the aggregation is equal to or higher than the lower limit, the poor solvent is maintained in a liquid state, and the cooling energy can be prevented.
  • An aggregation time is not particularly limited.
  • the aggregation time is usually 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours.
  • the aggregation step is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas, from the viewpoint of preventing oxidation and deactivation of the complex catalyst contained in the reaction solution and the aggregate.
  • the aggregation step is preferably performed by stirring the reaction solution and the poor solvent under neutral to acidic conditions, since it is not necessary to perform an operation such as a washing or neutralization treatment when the solution containing the aggregate after the aggregation is fed to the hydroformylation reaction zone.
  • the reaction solution withdrawn from the hydroformylation reaction zone is weakly acidic, and a solution obtained by mixing a poor solvent containing a mixed solution of water and alcohol with the reaction solution has a pH of about 4 to 7. Therefore, the aggregation operation can be performed without performing any particular pH adjustment.
  • a glass container or stainless steel container, and a SUS container with a stirrer, which can be sealed, are preferably used.
  • the aggregate precipitated by mixing the reaction solution withdrawn from the hydroformylation reaction zone with the poor solvent has adhesiveness under aggregation conditions.
  • the expression “having adhesiveness” means that the precipitated aggregate has an adhesive force sufficient to adhere to an inner surface of the mixing tank in the aggregation step of the present invention. Since the aggregate has adhesiveness as described above, the precipitated aggregate is separated from the solution in the mixing tank, and due to the adhesiveness, the aggregate adheres to the inner surface of the mixing tank, that is, a bottom surface or an inner wall of the mixing tank, a stirring blade, etc.
  • the reaction solution containing the high-boiling-point byproduct is withdrawn from the hydroformylation reaction zone to perform aggregation
  • the aggregate precipitated by the aggregation contains the complex catalyst and the high-boiling-point byproduct, and the presence of the high-boiling-point byproduct allows the aggregate to have adhesiveness.
  • the complex catalyst can be recovered at a high recovery ratio.
  • the lower limit of the distribution ratio of the high-boiling-point byproduct in the aggregate is preferably 4.0 mass % or more, more preferably 5.0 mass % or more, and further preferably 6.0 mass % or more.
  • the aggregation is preferably performed such that the upper limit of the distribution ratio of the high-boiling-point byproduct in the aggregate is usually 30 mass % or less, more preferably 20 mass % or less, and further preferably 10 mass % or less.
  • the distribution ratio of the high-boiling-point byproduct in the aggregate is preferably 4.0 mass % or more and 30 mass % or less, more preferably 5.0 mass % or more and 20 mass % or less, and still more preferably 6.0 mass % or more and 10 mass % or less, when the total mass of the high-boiling-point byproduct contained in the reaction solution withdrawn from the hydroformylation reaction zone is 100 mass %.
  • the distribution ratio can be controlled by adjusting aggregation conditions such as the composition of the poor solvent, the ratio of the poor solvent and the reaction solution, and the aggregation temperature.
  • the aggregate precipitated in the aggregation step and adhering to the inner surface of the mixing tank is recovered.
  • the recovered aggregate is preferably fed to the hydroformylation reaction zone.
  • the method for recovering the aggregate is not particularly limited, and it is preferable to recover the aggregate by dissolving the aggregate in a good solvent for the complex catalyst in the aggregate, since the operation is simple and the recovery ratio of the complex catalyst can be increased. Specifically, the solution in the mixing tank is withdrawn to leave only the aggregate, and the good solvent for the complex catalyst is added thereto to dissolve the aggregate.
  • the good solvent for the complex catalyst used in this case is not particularly limited.
  • the good solvent is preferably those described above as a reaction medium used in the hydroformylation reaction or an aldehyde, which is a product obtained by the hydroformylation reaction, since the aggregate solution can be directly fed to the hydroformylation reaction zone.
  • the good solvent include, when the raw material olefin is propylene, aldehydes such as n-butyl aldehyde and i-butyl aldehyde, and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • An amount of the good solvent to be used for dissolving the aggregate is not particularly limited, and it is preferable that the amount of the good solvent used to dissolve the aggregate is smaller, from the viewpoint of reducing the volume of the mixing tank.
  • the amount of the good solvent varies depending on the solubility of the catalyst with respect to the good solvent to be used and the content of the high-boiling-point compound in the aggregate, and the amount of the good solvent is generally preferably about 5 times to 100 times by mass with respect to the aggregate.
  • a temperature for dissolving the aggregate in the good solvent is preferably about 5° C. to 60° C.
  • the aggregate solution can be directly fed to the hydroformylation reaction zone, and if necessary, unnecessary components may be removed by a known separation operation such as distillation, or a solvent or a complex catalyst having high catalytic activity may be added and then fed to the hydroformylation reaction zone.
  • such a reaction solution containing the complex catalyst and the high-boiling-point byproduct is withdrawn from the hydroformylation reaction zone, and the poor solvent is added and mixed in the mixing tank to precipitate the adhesive aggregate containing the complex catalyst and the high-boiling-point byproduct, and the precipitated aggregate adheres to the inner surface of the mixing tank and is recovered.
  • an aldehyde which is produced by the method for producing an aldehyde of the present invention is used.
  • An alcohol can be produced by directly reacting an aldehyde with hydrogen, namely hydrogenation reaction, or bringing into hydrogenation reaction after dimerization.
  • reaction conditions thereof are usually a temperature of 60° C. to 200° C. and a hydrogen pressure of 0.1 MPaG to 20 MPaG.
  • the catalyst composition of the present invention contains: a catalyst; and a high-boiling-point byproduct.
  • the catalyst is a periodic table Group 8 to 10 metal-organophosphorus complex catalyst.
  • a content ratio of the high-boiling-point byproduct is 30 mass % or more, based on 100% of a total mass of the catalyst composition.
  • the catalyst composition of the present invention When the catalyst composition of the present invention satisfies the above configuration, the catalyst composition has adhesiveness, and the catalyst composition is recovered by adhering the catalyst composition to an inner surface of a reaction device such as a mixing tank, thereby improving the recovery ratio of the catalyst.
  • the method for obtaining the catalyst composition of the present invention is not particularly limited, and examples thereof include a method for obtaining an aggregate according to any of the methods of the first, second, and third embodiments of the method for producing an aldehyde of the present invention described above.
  • a catalyst same as the catalyst used in the first, second, and third embodiments of the method for producing an aldehyde of the present invention described above can be adopted as the catalyst.
  • a high-boiling-point byproduct same as those described in the first, second, and third embodiments of the method for producing an aldehyde of the present invention can be adopted as the high-boiling-point byproduct.
  • a catalyst same as the periodic table Group 8 to 10 metal-organophosphorus complex catalyst described in the first, second, and third embodiments of the method for producing an aldehyde of the present invention can be adopted as the periodic table Group 8 to 10 metal-organophosphorus complex catalyst.
  • a lower limit of the content ratio of the high-boiling-point byproduct is 30 mass % or more, preferably 40 mass % or more, more preferably 50 mass % or more, further preferably 60 mass % or more, and particularly preferably 70 mass % or more, with respect to 100% of the total mass of the catalyst composition, from the viewpoint that the catalyst composition has adhesiveness, and the catalyst composition is recovered by adhering the catalyst composition to the inner surface of the reaction device such as a mixing tank, thereby increasing the recovery ratio of the catalyst such as the complex catalyst.
  • an upper limit of the content ratio of the high-boiling-point byproduct is not particularly limited, and the content ratio may be preferably 97 mass % or less, more preferably 90 mass % or less, and further preferably 80 mass % or less, with respect to 100% of the total mass of the catalyst composition, from the viewpoint that the catalyst composition is easily precipitated as an aggregate.
  • a lower limit of the content ratio of the catalyst is not particularly limited, and the content ratio may be preferably 3 mass % or more, more preferably 10 mass % or more, and further preferably 20 mass % or more, with respect to 100% of the total mass of the catalyst composition, from the viewpoint that the catalyst composition is easily precipitated as an aggregate.
  • an upper limit of the content ratio of the catalyst is preferably 70 mass % or less, more preferably 60 mass % or less, still more preferably 50 mass % or less, further preferably 40 mass % or less, and particularly preferably 30 mass % or less, with respect to 100% of the total mass of the catalyst composition, from the viewpoint that the medium composition has adhesiveness, and the catalyst composition is recovered by adhering the catalyst composition to the inner surface of the reaction device such as a mixing tank, thereby increasing the recovery ratio of the catalyst such as the complex catalyst.
  • the catalyst composition of the present invention may contain other components such as a reaction solvent and an aldehyde, which is a target product of the hydroformylation reaction, in a content ratio of 10 mass % or less, and preferably 5 mass % or less with respect to the 100% of total mass of the catalyst composition, in addition to the high-boiling-point byproduct and the catalyst.
  • a reaction solvent and an aldehyde which is a target product of the hydroformylation reaction
  • the method for producing an aldehyde of the present invention is a method for producing an aldehyde including dissolving the catalyst composition of the present invention in a good solvent for the catalyst to obtain a catalyst solution, and subjecting an olefin to a hydroformylation reaction in the presence of the catalyst solution to obtain an aldehyde corresponding to the olefin.
  • a method for dissolving the catalyst composition of the present invention in a good solvent for the catalyst to obtain a catalyst solution is not particularly limited.
  • a method and conditions same as those of the method for obtaining an aggregate solution using the catalyst composition of the present invention in place of an aggregate in the recovery step of the method according to any of the first, second, and third embodiments of the method for producing an aldehyde of the present invention described above can be adopted.
  • the method for subjecting an olefin to a hydroformylation reaction in the presence of the catalyst solution to obtain an aldehyde corresponding to the olefin is not particularly limited.
  • conditions same as those exemplified in the hydroformylation reaction step in the method according to any of the first, second, and third embodiments of the method for producing an aldehyde of the present invention can be adopted.
  • Rhodium acetate aqueous solution (rhodium acetate concentration: 28 mass %) (trade name: rhodium acetate L, manufactured by N.E. CHEMCAT CORPORATION)
  • n-Butyl aldehyde (purity: 99% or more, manufactured by Mitsubishi Chemical Corporation)
  • Metanol (trade name: special grade reagent, Metanol, manufactured by FUJIFILM Wako Pure Chemical Corporation)
  • Phosphite ligand A bisphosphite ligand compound shown below, synthesized by a method described in WO2019/039565
  • a hydroformylation reaction of propylene was performed using rhodium acetate as a periodic table Group 8 to 10 metal compound, and a phosphite ligand A as an organophosphorus ligand.
  • a reaction solution was withdrawn from a hydroformylation reaction zone, and a light-boiling-point component was distilled off using a distillation method.
  • a composition of the reaction solution after distillation and before being subjected to an aggregation treatment was as follows.
  • An amount of rhodium atoms in the complex catalyst in the reaction solution was determined by X-ray fluorescence analysis.
  • An amount of n-butyl aldehyde was determined by a gas chromatography internal standard method.
  • An amount of the phosphite ligand A was determined by a high-performance liquid chromatography external standard method.
  • Rhodium atoms in complex catalyst 373 mass ppm
  • a glass container with an electromagnetic induction stirrer having a volume of 0.5 L was used as a mixing tank.
  • the mixture was kept at a temperature of 10° C. for 2 hours while being stirred at 500 rpm to perform the aggregation treatment, thereby precipitating a rhodium complex together with a high-boiling-point byproduct.
  • the precipitated aggregate adhered to an inner wall of the mixing tank, a stirring blade, etc., thereby solid-liquid separating the aggregate and the mother liquid.
  • the adhering aggregate had a property of an adhesive substance.
  • the mother liquid was withdrawn from the mixing tank, and then 400 mL of n-butyl aldehyde was introduced into the mixing tank to dissolve the aggregate adhering to the inside of the mixing tank at room temperature, and the aggregate solution was recovered.
  • a content M1 (unit: mg) of the high-boiling-point byproduct contained in the aggregate solution and a content M2 (unit: mg) of the high-boiling-point byproduct contained in the mother liquid withdrawn from the mixing tank were measured by the gas chromatography internal standard method, and a distribution ratio of the high-boiling-point byproduct in the aggregate was calculated using the following formula. As a result, the distribution ratio was 9.2 mass %.
  • Distribution ⁇ ratio ⁇ ( mass ⁇ % ) ⁇ of ⁇ high - boiling - point ⁇ byproduct M ⁇ 1 / ( M ⁇ 1 + M ⁇ 2 ) ⁇ 100
  • the rhodium recovery ratio was measured according to the following procedure.
  • Rhodium ⁇ recovery ⁇ ratio ⁇ ( mass ⁇ % ) ⁇ R ⁇ 1 / ( R ⁇ 1 + R ⁇ 2 ) ⁇ 1 ⁇ 0 ⁇ 0
  • the aggregate solution and toluene as a solvent were mixed, and 54 ml of the obtained mixed solution was put into an upper and lower stirring type autoclave having a volume of 0.2 L in a nitrogen atmosphere, and the autoclave was sealed.
  • the composition of the reaction solution before the hydroformylation reaction was as follows.
  • Rhodium atoms in complex catalyst 152 mass ppm
  • Phosphite ligand A 5929 mass ppm
  • An apparent reaction rate (a rate constant) of the hydroformylation reaction which was calculated based on a propylene conversion ratio, a propane selection ratio, an aldehyde selection ratio, an N/I ratio (a ratio of n-butyl aldehyde to i-butyl aldehyde) of a target product butyraldehyde, a half-life of propylene, and a reduction ratio of carbon monoxide during the hydroformylation reaction when the hydroformylation reaction of propylene was performed, was determined.
  • the evaluation results are shown in Table 2.
  • an aldehyde production experiment was performed by the following procedure using a commercially available rhodium catalyst.
  • rhodium catalyst As a commercially available rhodium catalyst, a (1,5-cyclooctadiene) acetate rhodium dimer (trade name: Rh 2 (cod) 2 (OAc) 2 , manufactured by N.E. CHEMCAT CORPORATION) was used.
  • Rh 2 (cod) 2 (OAc) 2 , a bisphosphite ligand A, and toluene as a solvent were mixed, 54 mL of the obtained mixed solution was put in an upper and lower stirring type autoclave having a volume of 0.2 L in a nitrogen atmosphere, and the autoclave was sealed.
  • the composition of the reaction solution before the hydroformylation reaction is shown in Table 2.
  • Example 1 An aggregation treatment was performed under the same conditions as in Example 1 except that a composition of a reaction solution before the aggregation treatment or a composition of a poor solvent (water/methanol) was changed as shown in Table 1, thereby obtaining an aggregate containing a rhodium complex catalyst. Further, an aldehyde was produced using the obtained aggregate under the same conditions as in Example 1. The evaluation results are shown in Table 1.
  • FIG. 2 A An appearance photograph of the mixing tank after aggregation, which was obtained in Example 2, was shown in FIG. 2 A .
  • an aggregate adhering to the inside of the mixing tank and the reaction solution after the reaction exhibited a solid-liquid separation state.
  • a crystallization treatment was performed under the same conditions as in the aggregation treatment in Example 1 except that a composition of a reaction solution before the crystallization treatment and a composition of a poor solvent (water/methanol) were changed as shown in Table 1, and a crystallized product containing a rhodium complex catalyst was obtained.
  • FIG. 2 B An appearance photograph of the mixing tank after the crystallization treatment, which was obtained in Comparative Example 1, was shown in FIG. 2 B .
  • the crystallization treatment solution was not solid-liquid separated and formed a uniform slurry.
  • the adhesion of the crystallized product to the inside of the mixing tank was not confirmed.
  • the obtained slurry was solid-liquid separated using a commercially available polytetrafluoroethylene membrane filter having a hole diameter of 0.5 ⁇ m.
  • the amount R1 (in terms of rhodium atom, unit: mg) of the rhodium complex catalyst contained in the solution of the crystallized product and the amount R2 (in terms of rhodium atom, unit: mg) of the rhodium complex catalyst in the recovered crystallized product were measured by a fluorescent X-ray analysis method, and the rhodium recovery ratio was calculated using the following formula, and as a result, the recovery ratio was 9.3 mass %.
  • Rhodium ⁇ recovery ⁇ ratio ⁇ ( mass ⁇ % ) ⁇ R ⁇ 1 / ( R ⁇ 1 + R ⁇ 2 ) ⁇ 1 ⁇ 0 ⁇ 0
  • Example Unit 1 2 3 4 5 Solution composition Rhodium atoms Mass ppm 373 379 367 386 386 of reaction solution in complex catalyst Phosphite ligand Mass ppm 12006 12749 10130 12007 12007 in complex catalyst n-Butyraldehyde Mass % 10.6 10.1 10.9 9.9 99 Aggregation or Aggregation or 10 10 10 10 crystallization crystallization temperature conditions Aggregation or hr 120 120 120 120 120 crystallization time Composition of poor solvent Mass % 20/80 20/80 20/80 20/80 15/85 (water/methanol) Mass ratio of — 9.00 9.00 9.00 9.00 poor solvent/reaction solution Distribution ratio of Mass % 5.4 6.2 9.1 9.2 5.7 high-boiling-point byproduct in aggregate or crystallized product Form of aggregation — Solid-liquid Solid-liquid Solid-liquid Solid-liquid Solid-liquid Treatment solution or separation separation separation separation crystallization treatment solution (visual observation) Property of aggregate or — Adhes
  • the distribution ratio of the high-boiling-point byproduct in the aggregate was significantly increased and the aggregation conditions were controlled such that the aggregate having adhesiveness was precipitated, so that the solid-liquid separation proceeded after the aggregation treatment, and almost all of the precipitated aggregates adhered to the mixing tank, specifically, the stirring blades and the introduction pipe in the glass container. Further, by dissolving and recovering the adhesive product from the mixing tank, the rhodium complex catalyst could be recovered at a high yield.
  • the rhodium complex catalyst recovered in Example 1 had a catalytic performance equivalent to that of a complex catalyst using a commercially available rhodium catalyst in the production of aldehyde.
  • Comparative Example 1 the distribution ratio of the high-boiling-point byproduct in the crystallized product was low, so that the obtained crystallized product was crystallized as a crystal having no adhesiveness.
  • the form of the crystallization treatment solution was a uniform slurry state.
  • the recovery ratio of the rhodium complex catalyst was low.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US18/743,198 2021-12-14 2024-06-14 Method for producing aldehyde, method for producing alcohol, and catalyst composition Pending US20240327325A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021-202681 2021-12-14
JP2021202681 2021-12-14
PCT/JP2022/044805 WO2023112762A1 (ja) 2021-12-14 2022-12-06 アルデヒドの製造方法及びアルコールの製造方法、並びに触媒組成物

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/044805 Continuation WO2023112762A1 (ja) 2021-12-14 2022-12-06 アルデヒドの製造方法及びアルコールの製造方法、並びに触媒組成物

Publications (1)

Publication Number Publication Date
US20240327325A1 true US20240327325A1 (en) 2024-10-03

Family

ID=86774290

Family Applications (1)

Application Number Title Priority Date Filing Date
US18/743,198 Pending US20240327325A1 (en) 2021-12-14 2024-06-14 Method for producing aldehyde, method for producing alcohol, and catalyst composition

Country Status (5)

Country Link
US (1) US20240327325A1 (https=)
EP (1) EP4450484A4 (https=)
JP (2) JP7639833B2 (https=)
CN (1) CN118414322A (https=)
WO (1) WO2023112762A1 (https=)

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415906A (en) 1964-05-29 1968-12-10 Hooker Chemical Corp Phosphite phospholane and phosphorinane compounds
DE2912230B1 (de) * 1979-03-28 1980-10-09 Union Carbide Corp Verfahren zur Rueckgewinnung und Reaktivierung gebrauchter Rhodium- und Phosphin-enthaltender Katalysatoren aus Reaktionsprodukten der Rhodium-katalysierten Oxosynthese
JPS5923858B2 (ja) * 1981-01-22 1984-06-05 三菱化学株式会社 ロジウム錯体の取得方法
GB8334359D0 (en) 1983-12-23 1984-02-01 Davy Mckee Ltd Process
US4599206A (en) 1984-02-17 1986-07-08 Union Carbide Corporation Transition metal complex catalyzed reactions
US4737588A (en) 1984-12-28 1988-04-12 Union Carbide Corporation Transition metal complex catalyzed reactions
US5648554A (en) * 1995-04-12 1997-07-15 Mitsubishi Chemical Corporation Method for producing aldehydes
JP3959754B2 (ja) * 1995-04-12 2007-08-15 三菱化学株式会社 アルデヒド類の製造方法
JP3888008B2 (ja) * 1999-10-12 2007-02-28 三菱化学株式会社 第８族貴金属及び／又は有機ホスファイト化合物の回収方法
CN100339158C (zh) * 2003-11-20 2007-09-26 三菱化学株式会社 铑络合物催化剂的回收方法
JP4534732B2 (ja) 2004-11-25 2010-09-01 三菱化学株式会社 ヒドロホルミル化方法
JP4548103B2 (ja) * 2004-11-30 2010-09-22 三菱化学株式会社 ヒドロホルミル化方法
JP2013147445A (ja) * 2012-01-18 2013-08-01 Mitsubishi Chemicals Corp アルデヒドの製造方法
JP7180603B2 (ja) 2017-08-24 2022-11-30 三菱ケミカル株式会社 ジヒドロキシビフェニル化合物、ビスホスファイト化合物、触媒、アルデヒド類の製造方法及びアルコールの製造方法
WO2019098242A1 (ja) 2017-11-15 2019-05-23 三菱ケミカル株式会社 アルデヒドの製造方法及びアルコールの製造方法

Also Published As

Publication number Publication date
JP2025010331A (ja) 2025-01-20
JPWO2023112762A1 (https=) 2023-06-22
EP4450484A1 (en) 2024-10-23
EP4450484A4 (en) 2025-08-27
WO2023112762A1 (ja) 2023-06-22
CN118414322A (zh) 2024-07-30
JP7639833B2 (ja) 2025-03-05

Similar Documents

Publication Publication Date Title
TWI586644B (zh) 氫甲醯化方法
JP5180819B2 (ja) ビスホスファイトおよび第８〜１０族金属化合物を用いたアルデヒドの製造方法、並びに該ビスホスファイト
ZA200409050B (en) Method for the rhodium-catalysed hydroformylation of olefins with reduction of rhodium losses
MXPA05001396A (es) Procedimiento para la obtencion de aldehidos mediante la hidroformilacion de compuestos olefinicamente insaturados, catalizado con complejos de metal no modificados en presencia de esteres ciclicos de acido carboxilico.
RU2660899C2 (ru) Кристаллический сольват и несольватированные формы 6,6'-[[3,3',5,5'-тетракис(1,1-диметилэтил)-[1,1'-бифенил]-2,2'-диил]бис(окси)]бис-дибензо[d,f][1,3,2]-диоксафосфепина
US7420092B2 (en) Process for producing aldehyde
EP3712126B1 (en) Method for producing aldehyde and method for producing alcohol
TW201925153A (zh) 氫甲醯化方法
US6583324B2 (en) Process for producing aldehyde
JPH11130718A (ja) アルデヒド類の製造方法及びこれに用いるビスホスファイト
US20240327325A1 (en) Method for producing aldehyde, method for producing alcohol, and catalyst composition
CN108698962B (zh) 将烯烃转化成醇、醚或其组合的方法
US20240308947A1 (en) Method for producing aldehyde
US9382180B2 (en) Hydroformylation process
US10793497B2 (en) Dihydroxybiphenyl compound, bisphosphite compound, catalyst, production method of aldehydes, and production method of alcohol
US20100137623A1 (en) Stable catalyst precursor of rh complex catalysts
JP2008031125A (ja) アルデヒドの製造方法
JP4534732B2 (ja) ヒドロホルミル化方法
US11370737B2 (en) Co-feeding ethylene with allyl alcohol in hydroformylation to make 1,4-butanediol and n-propanol
JP4548103B2 (ja) ヒドロホルミル化方法
JP7355230B2 (ja) アルデヒドの製造方法及び触媒の製造方法
JPH11130720A (ja) アルデヒド類の製造方法
JP2006169131A (ja) ヒドロホルミル化方法
JP4595495B2 (ja) アルデヒドの製造方法
CN121532373A (zh) 用于改善基于铑/亚磷酸酯的均相加氢甲酰化催化剂活性的方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: MITSUBISHI CHEMICAL CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MIYAKE, MASASHI;SATO, TAKASHI;SIGNING DATES FROM 20240520 TO 20240522;REEL/FRAME:067726/0572

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION